KR20060096389A - Glass-like carbon deformed molded article, process for producing the same, and joint structure for jointing a connecting member to a glass-like carbon hollow molded article - Google Patents

Abstract

Provided is a method for producing a release-shaped glass-like carbon component having a deformed tube shape, typically an ellipse or a partial circle, and a straight portion, or a glass-shaped carbon release molded article which can produce a bent pipe with relatively easy and high dimensional accuracy. . A step of molding the thermosetting resin to obtain a thermosetting resin molded article, a step of plastically deforming the thermosetting resin molded body in a heated state to obtain a thermosetting resin release article, and a step of carbonizing the obtained thermosetting resin release article. It may include.

Description

Glass-like carbon release molded article, manufacturing method thereof and coupling structure of connecting member to glass-like carbon molded article HOLLOW MOLDED ARTICLE}

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows one Embodiment of the plastic deformation process which obtains the thermosetting resin mold release tube from the thermosetting resin cylindrical molded object which concerns on this invention, a is a state before plastic deformation, and b is a state after plastic deformation.

2 is a perspective view of a release tube made of a thermosetting resin according to the present invention.

Fig. 3 is an explanatory view showing one embodiment of a carbonization step of obtaining a glassy carbon release tube from a thermosetting resin release tube according to the present invention, where a is a state before carbonization treatment and b is a state after carbonization treatment.

Fig. 4 is an explanatory view showing one embodiment of a carbonization step of obtaining a glassy carbon release tube from the thermosetting resin release tube of the comparative example, where a is a state before the carbonization treatment and b is a state after the carbonization treatment.

Fig. 5 is a cross-sectional view showing an example of a cross-sectional shape of a thermosetting resin release tube according to the present invention, where a is a rectangular shape having four corners and b is a long hole shape (track shape) in which two sides are parallel.

It is sectional drawing which shows the example of the cross-sectional shape of the tube longitudinal direction of the thermosetting resin bending pipe which concerns on this invention.

It is explanatory drawing which shows the coupling structure of the connection member to the hollow glass member made from glassy carbon which concerns on this invention, a is a front view, b is an X-X sectional enlarged view of a.

FIG. 8: is explanatory drawing of the connection member shown in FIG. 7, a is front view, b is top view.

It is sectional drawing which shows the coupling structure of the connection member to the conventional glassy carbon hollow molded object.

10 is a cross-sectional view for explaining the manufacturing method of the present invention, (a) is a view showing a pipe made of a straight tube thermosetting resin, (b) is a view showing a shape filled with sea sand in a pipe made of a straight pipe thermosetting resin, (c) Is a figure which shows the shape which formed the bending part by plastic deformation.

* Explanation of symbols for the main parts of the drawings

1: Cylindrical molded body made of thermosetting resin

2: round bar jig

3: release tube made of thermosetting resin

4: phenolic resin release cylinder

5: phenolic resin plate

6: glassy carbon release tube

7: graphite core

8: glass carbon release tube

9: tube

10: pipe

11: Blow molded product made of glassy carbon

12: connecting member

13: sealing material

14: retention member

15: fastening means

16: tube end

17: sleeve part

18: flange

19: elastic member

12: mounting groove

21: home

22: bolt hole

23: through hole

24: V-shaped groove

25: bolt hole

26: Bolt

27: nuts

41: straight pipe thermosetting pipe

42: maritime

43: cotton

44: thermosetting resin bent pipe

TECHNICAL FIELD This invention relates to the glassy carbon release molded object suitable as a part material used under high temperature, corrosive environment, and its manufacturing method, and also the coupling structure of the connection member to a glassy carbon molded object.

Free carbon has heat resistance of 2000 ° C. or higher in an inert atmosphere, and exhibits excellent corrosion resistance against hydrogen fluoride and fluorine. Therefore, even when handling a corrosive gas, such as a semiconductor manufacturing apparatus, the component parts of a CVD apparatus (a chamber of a Si wafer heat processing apparatus, or a gas ejection nozzle for blowing out the reaction gas used as a film-forming material on a wafer), generation of an impurity does not occur. It is contemplated to apply it to apparatus components that need to be small, to various other reaction vessels, and to pipes for supplying and discharging gas or liquid to the reaction vessels. This glassy carbon is generally produced by carbonizing and firing a molded body of a thermosetting resin such as a furan resin or a phenol resin at a high temperature.

In addition, since the glassy carbon itself cannot be welded or adhesively bonded, thermosetting resins such as furan resins and phenolic resins are generally molded into shapes close to the final product when the glassy carbon parts are manufactured (when the product is a tube). Molded into a tubular shape), and the thermosetting resin molded body is subjected to heat treatment and carbonization in an inert atmosphere at a high temperature (usually 1000 ° C. or higher).

However, glassy carbon has a problem in manufacturing technology in which the formability of the thermosetting resin as a raw material is low and shrinkage of about 20% occurs in carbonization, and it is not easy to mold a complicated part with high precision.

For example, a glass-like carbon-shaped molded body (cylindrical) having a simple circular cross section can be manufactured by a conventional method such as centrifugal molding using a thermosetting resin. However, in order to manufacture various components such as semiconductor film forming apparatus from glassy carbon, The release molded body of this non-circle shape is also needed. However, it is in principle impossible to produce such a release molded body by centrifugal molding.

Here, as shown in FIG. 5, the glass-shaped carbon shaped molded object tube which this invention targets is rectangular in which the cross section (cross section orthogonal to a pipe-axis direction) shape of the pipe 9 is curved, and two sides are parallel. An elongated hole shape (track shape), an elliptical shape, or the like, or a pipe having a bent portion as shown in FIG.

In the manufacture of cylindrical or shaped tubular glassy carbon parts, cores are generally used to ensure dimensional accuracy of the product. Here, the core is a component for maintaining the product shape, and at least a part of the dimension is designed to be almost equal to a part of the product dimension after the carbonization treatment, that is, the shrinkage. And it inserts and is used inside the thermosetting resin molding before carbonization process, and has a function which adjusts a product shape and a dimension to a predetermined range by supporting a product from inside (refer Japanese Unexamined-Japanese-Patent No. 2002-179463).

For example, in the case of producing cylindrical glassy carbon, carbonization treatment is carried out in a state in which a graphite cylinder having an outer diameter smaller than the inner diameter and having an outer diameter substantially equal to the inner diameter of the glassy carbon cylinder after carbonization is inserted as a core inside the thermosetting resin cylinder. Is carried out.

Japanese Unexamined Patent Application Publication No. 2000-313666 proposes a method for producing a glass-like carbon cylinder in which a thermosetting resin molded article having a cylindrical shape is formed, bonded to each other to form a cylindrical molded article, and carbonized. However, Japanese Unexamined Patent Application Publication No. 2000-313666 does not mention the production of a release tube such that the cross section is an ellipse or consists of a partial circle and a straight portion. In addition, according to the proposed manufacturing method, it is inherently difficult to manufacture the release tube portions with high dimensional precision and to accurately position and join them.

In addition, in order to manufacture a glassy carbon curved pipe (glass-like carbon curved pipe) having a bent portion, a method starting from a thermosetting resin bent pipe having a bent portion as disclosed in Japanese Patent Laid-Open No. 1999-322428 Although it employs, there is a drawback of requiring a large and complicated mold or complicated molding process, and it is difficult to manufacture with high dimensional accuracy in nature and to accurately position and join them.

Moreover, when using a glassy carbon shaped molded object as a pipe for piping connected to a chamber or a reaction container, it is preferable that a joined part is not possible. This is because the joint line often causes dimensional deformation, residual stress, and dust generation.

On the other hand, the core is also a problem in terms of dimensional accuracy. The drawback of the method of using the core is that the gap between the core and the thermosetting resin molded product as a product is large at the time of starting the carbonization treatment, so that the effect of correcting the dimensional correction by the core is not sufficient. That is, since the carbonization process is roughly completed when the core and the product come into contact with each other, it is difficult to sufficiently correct the dimensions even by the core when the product is greatly deformed by that time. This difficulty is remarkable when the product is a release tube.

By the way, when the above-mentioned glassy carbon molded body is used in a container or the like, a sealing structure in which fluid does not leak generally is required for the opening (supply port) or the opening (pipe end opening) of the glassy carbon pipe part. That is, the removable cover which seals the opening part of the hollow part of a glass-shaped carbon molded object, the flange with a nozzle, or the connection member (connection flange) used when connecting and installing another member.

It is possible to manufacture a hollow glassy carbon molded article having a cover or a flange at its opening. However, in the case of a cover, depending on the use, it may be necessary to remove the cover, or may require processing such as attaching a nozzle to the cover. From application to such a use, the glass-shaped carbon molded object provided with the removable cover (including the cover processed by attaching a nozzle etc. beforehand) is calculated | required.

On the other hand, since glassy carbon is a brittle material, tensile or bending strength is inferior to ceramic materials used in this field such as alumina and silicon carbide. Therefore, as a sealing method of the flange portion such as the O-ring method shown in Fig. 9 used as a general pipe material, the cover (material is glassy carbon, stainless steel, quartz, etc.) 31 for fastening the flange portion 32 The fastening portion indicated by the arrow 33 may cause a large stress to break the flange 32 made of glassy carbon. In addition, there is a concern that a fastening with a weak force cannot secure sufficient sealing property. In the drawings, 34 denotes a hollow tubular molded body, and 35 denotes an O-ring, respectively.

Therefore, although it is conceivable to increase the thickness of the hollow molded article made of glassy carbon to improve the strength, in the case of glassy carbon, it is the upper limit to form a thickness of about 3 to 4 mm, which is not sufficient to improve the strength. The thickness is limited because a large amount of gas is generated in the step of carbonizing the raw material resin (thermosetting resin such as a phenol resin), so that when the thickness is too large, cracks or splitting occur.

Moreover, as a connection of the pipe end of a general pipe material, the connection structure proposed by Unexamined-Japanese-Patent No. 2004-19832, for example is mentioned. When the method is applied to the hollow glassy carbon molded body described above, the flange of the glassy carbon hollow molded body as described in the case of FIG. 9 in order to apply a force for fastening the O-ring between the flange and the intermediate flange of the pipe. It is necessary to apply a large tensile stress to it, and as a result, a damage is feared. On the contrary, it is feared that the sealing cannot be stopped if the sealing is loosely performed so that the glassy carbon hollow molded body does not break. Further, when the cross section orthogonal to the hollow direction (tube axis direction) of the glass-shaped carbon hollow molded body is not a circle (long circle or ellipse), since the rigidity of the parallel portion of the long circle or the large arc portion of the ellipse is partially reduced, The sealing force may distort the parallel portion of the long circle of the glass-like carbon-shaped hollow molded body or the large arc portion of the ellipse, resulting in incomplete sealing.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a release-like tubular glassy carbon component or a bent pipe having a cross-sectional shape, typically an ellipse, a partial circle, and a straight portion, and relatively high dimensional accuracy. It is to provide a method for producing a glassy carbon release molded article which can be produced by the present invention, and a glassy carbon release molded article. In addition, it is possible to remove the connecting member as a flange or a connecting member or a cover used for connecting other members to the open end of the hollow glass-like carbon molded article having a thin thickness or a cross section other than circular, which is insufficient in strength, but also with good sealing properties. It is providing the coupling | bonding structure of the connection member to the glassy carbon molded object so that it can install.

In order to achieve the above object, the manufacturing method of the glassy carbon-form molded article according to the present invention comprises the steps of molding a thermosetting resin to obtain a thermosetting resin molded body, and plastically deforming the thermosetting resin molded body in a heated state. And a step of carbonizing the obtained thermosetting resin mold release body.

It is possible to obtain a glassy carbon release tube by using the thermosetting resin molded article as a cylindrical molded article and the thermosetting resin modified article as a thermosetting resin release tube.

The thermosetting resin molded body may be a straight tube thermosetting resin pipe, and the plastic deformation step is a process of forming a bent portion by applying a bending force while heating a portion to be bent of the thermosetting resin pipe in a heated state. It is possible to obtain glassy carbon bent pipes.

The manufacturing method of the glassy carbon mold release molded object which concerns on this invention performs the said plastic deformation process at the temperature (T degreeC) which satisfy | fills following formula (1), when the glass transition point of a thermosetting resin molded object is set to Tg (degreeC). It is preferable that Tg of the said thermosetting resin molded object is 25 degreeC or more and 100 degrees C or less.

Moreover, the manufacturing method of the glassy carbon mold release molded object which concerns on this invention can include the process of forming a flange in the one side or both sides of the plastic deformation | transformation thermosetting resin release tube.

In the case of obtaining a glassy carbon release tube by the method of the present invention, in the carbonization step, it is preferable to arrange and carbonize a core having a carbonization shrinkage ratio substantially the same as that of the thermosetting resin release tube in the hollow portion of the thermosetting resin release tube. Moreover, it is preferable that the said core consists of a thermosetting resin of material substantially the same as the said thermosetting resin release tube.

The glassy carbon release tube according to the present invention does not have a joint in a direction parallel to the longitudinal direction, and the glassy carbon curved pipe according to the present invention has a seamless curved portion.

Moreover, the coupling structure of the connection member to the glassy carbon release tube which concerns on this invention is a coupling structure which couples and installs a connection member in the opening edge part of a hollow glassy carbon release tube, and can be inserted inside a glassy carbon release tube. A connecting member formed integrally with the flange portion on the outer circumference of the sleeve portion, a sealing material disposed on the outer circumference of the opening end of the glass-shaped carbon release tube, and a holding member for sandwiching the sealing material between the flange portion of the connecting member. The retaining member is fastened to the flange portion via the fastening means, and the sealing member held between the retaining member and the flange portion is compressed to engage the open end of the glass-shaped carbon release tube and the connecting member.

In the coupling structure of the connection member to the said glass-shaped carbon release tube, it is preferable to arrange | position a flexible member in at least one part of the outer peripheral surface of the sleeve part inserted inside a glassy carbon molded object. In addition, it is preferable that the connecting member and the holding member are made of metal or ceramic.

The coupling structure of the connecting member to the glassy carbon release tube according to the present invention can also be applied to a hollow glassy carbon shaped article.

Hereinafter, the present invention will be described in detail.

The manufacturing method of the glassy carbon mold release molded object of this invention is the process of shape | molding a thermosetting resin, and obtaining a thermosetting resin cylindrical molded object, and carrying out plastic deformation in the state which heated the thermosetting resin cylindrical molded object, and obtaining a thermosetting resin mold release body. And a step of carbonizing the obtained thermosetting resin release product.

In the step of obtaining the thermosetting resin cylindrical molded product, the raw material resin is molded into a cylindrical shape, but the molding method in this case is not particularly limited, and known techniques such as centrifugal molding, injection molding, and extrusion molding can be employed. It is preferable to employ especially the centrifugal molding method among these molding methods. For this reason, in the centrifugal molding method, since the raw material resin in the molten state flows to the inner surface side of the molding mold and hardens by centrifugal force, the molding of the cylindrical object is easy, the dimensional accuracy of the molded body is high, and the inner surface side at the time of molding is Since it is open | released, gas removal can also be performed favorably, and it is an advantage that there is little junction line as an embodiment of the use of the glass-shaped carbon release pipe | tube and a bending pipe which are final products. Moreover, as raw material resin, well-known thermosetting resin, such as a phenol resin and furan resin, can be employ | adopted preferably, for example.

In the process of obtaining the thermosetting resin deformable body, although the thermosetting resin cylindrical molded object obtained above is plastically deformed in the state heated, the means of plastic deformation is not specifically limited.

For example, when obtaining a release tube, using a divided mold having a release tube shape while applying a load with a press while heating, at least two rod-like jig is provided on the inner circumferential surface of the cylindrical molded body made of thermosetting resin, and heated. And a means for pressing the rod-like jig in the circumferential direction. BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows one Embodiment of the latter plastic working method. In the plastic working shown in FIG. 1, the round bar jig 2 is provided while heating the cylindrical molded body 1 made of a thermosetting resin to a predetermined temperature (see FIG. 1A). Subsequently, processing is performed by pressing in the circumferential direction by a means (not shown) by pressing the opening bar jig 2 (not shown) while heating the thermosetting resin cylindrical molded body 1 to a predetermined temperature. The release tube 3 made of thermosetting resin obtained by such a process is shown in FIG.

In the case of obtaining a bent pipe, for example, a method of heating at least a bent portion, applying a load by a press using a mold having a bent portion to fit the split mold, and a bent portion of the thermosetting resin pipe The method of pressing and bending as it is, or the method of installing a jig and pressing the pipe parts on both sides thereof from the starting point, may be mentioned.

Said plastic working process is demonstrated more concretely.

In general, it is known that a cylindrical molded article made of a thermosetting resin is not easy because of lack of rigidity. Therefore, it is not easy to manufacture a complicated shaped molded object (release tube) and a bent pipe by joining the thermosetting resin molded object divided into many previously. Here, as a result of various tests on the production of the release molded articles of the thermosetting resin, the present inventors have found that the cylindrical molded articles made of the thermosetting resin are easily plastically deformed when heated and applied above the glass transition point (hereinafter referred to as Tg). Discovered and completed the present invention.

In this case, it is preferable that the temperature T (° C) of the thermosetting resin molded body at the time of plastic deformation satisfies the range of (Tg + 5 ° C) to 150 ° C. In the case of a temperature lower than this range, that is, when the temperature difference (T-Tg) is smaller than 5 DEG C, a large force is required for plastic deformation, which causes damage. Therefore, the temperature higher 5 degreeC or more than Tg is preferable. When obtaining the bending pipe which bent the straight pipe, the temperature 10 degreeC or more higher than Tg is preferable.

The upper limit temperature is preferably 150 ° C. or lower in consideration of the curing rate of the thermosetting resin. The higher the temperature, the higher the deformability of the thermosetting resin and the easier the deformation operation is. However, if the temperature is too high, the curing reaction proceeds rapidly and conversely, the time used for the deformation operation is shortened. Preferably it is 120 degrees C or less, Especially preferably, it is 90 degrees C or less.

As for the thermosetting resin cylindrical molded object provided for plastic deformation, it is preferable that Tg is 100 degrees C or less, Preferably it is 60 degrees C or less. When Tg is high, it is necessary to heat to high temperature in order to plastically deform. For this reason, since deformation operation becomes difficult and hardening reaction advances rapidly during plastic deformation operation, deformation becomes difficult. The lower limit of the Tg is not particularly limited, and generally the lower one is preferable. However, when too low, since the intensity | strength at room temperature is insufficient and handling becomes difficult, it is preferable to have Tg more than room temperature and 25 degreeC or more.

The plastic deformation process will be described separately in the case of obtaining a glassy carbon release tube and in the case of obtaining a bent pipe.

<Glass-like carbon release tube>

Plastic deformation, as described above, is applied to the mold by applying a load by pressing in a state where the thermosetting resin cylindrical molded body is heated by using a split mold having a shape of a release tube, or at least 2 provided on the inner circumferential surface in a heated state. Although it implements by the processing means which pushes a rod-shaped jig in radial direction, there exists a restriction | limiting in the range which plastically deforms the cylindrical molded object made of thermosetting resin. In other words, plastic deformation exceeding the limit is a deformation limit in which defects such as fracture and cracking occur. The radius of curvature before and after the plastic deformation is R and R ', the ratio (R' / R) is t, and the ratio (thickness / R) of the radius R before the thickness and plastic deformation is w. Assuming that the central portion of the thickness is neutral with respect to the deformation (dimensions do not change), plastic deformation occurs evenly on the outside and the inside, and the change in the thickness can be neglected. lo, li) is represented by the following formula.

lo = (t + w / 2) / [t (1 + w / 2)]

li = (t-w / 2) / [t (1-w / 2)]

Although it depends also on the property of resin, in general, it is preferable that change rate lo-li is 10% or less, Preferably it is 5% or less. For example, when a part of a cylinder having a thickness of 320 mm and a thickness of 3 mm is plastically deformed into a release tube having an arc having a thickness of 60 mm, the change rate of the outer circumference and the inner circumference becomes about 4%.

As stated in the above equation, the rate of change of the outer circumference and the inner circumference also affects the ratio of thickness and R. In other words, the larger the thickness, the larger the rate of change. In the above example, a thickness of 3 mm to 6 mm causes about twice the change with the same deformation. That is, it is preferable that thickness is relatively thin in the range which there is no problem in component design. In the case of causing a large plastic deformation of 10% or more, the resin molded body is not preferable because of a high fear of defects. The rate of plastic deformation is not particularly limited, but in general, a good result is obtained in a state where a load is applied over several hours to several minutes. If a sharp deformation occurs, the resin may deteriorate.

<Bending pipe>

As described above, the formation of the bent portion by plastic deformation is performed by heating a portion to be bent and applying a load by pressing using a divided mold having a bent portion to fit the divided mold, and bending of a straight tube thermosetting resin pipe. It is carried out by pressing and bending the part to be made as it is, or by installing a jig and pressing and bending the pipe parts on both sides thereof as a starting point. At this time, it is preferable to perform heating with respect to the thermosetting resin pipe only to the part to be bent. This is because unheated areas deform when heated over a large area. Specifically, a region portion of [region corresponding to the bent portion (elbow portion) after deformation] + [about 5 to 30 mm at each end thereof] is preferable.

Here, when bending a pipe made of a straight tube thermosetting resin by applying a bending force, it is important to fill the pipe with powder in advance in order to prevent the bent hollow portion from being deformed.

The effect by the filling of this powder is demonstrated. When the thermosetting resin pipe filled with nothing in the hollow part is bent to a temperature at which it can soften and bends, a stress that is pulled out on the outer peripheral side of the bent part is generated, so that the hollow part of the pipe is deformed and the inner diameter becomes small. In severe cases, it cannot be used as a piping component. On the contrary, when the powder having a moderate fluidity is filled and bent in the hollow portion of the pipe, the powder can form a bent portion without substantially deforming since the bending is continued while resisting the force for deforming the pipe. Here, "suitable fluidity" means a range of fluidity that makes it easy to enter and exit the pipe.

Suitable powders for this purpose include carbon powders such as various sands, silica and graphite, ceramic powders, glass powders and plastic powders. Among them, maritime is easy to use easily. Very fine and highly compressible powders such as wheat flour or powders that are simply deformed, such as expanded styrene powder, are not preferable. The particle size of the powder is preferably about 0.1 to 1mm.

Although the part which fills powder does not have a problem even if it is a part which plastically deforms in principle, it is simpler and more practical to fill the whole pipe actually. The filling rate is naturally full. If the filling rate is lower than this, the filling effect is lost, and if the filling rate is high, it may be impossible to follow the deformation. In practice, the filling rate is about 70 to 90%.

By the way, although the shape and the magnitude | size of the curved part of a thermosetting resin curved pipe should be set suitably according to a component specification, in this invention, the value of [thickness / pipe outer diameter] is 1/20 or more, More preferably, 1 / It is recommended to apply to more than 10 pipes. If this value is small, the rigidity of the whole pipe is low, so that the pipe is likely to break in the plastic deformation step.

The value of the inner curvature radius of the bent portion of the thermosetting resin bent pipe is preferably equal to or larger than the pipe outer diameter. This is because, if the inner curvature radius is made too small, the amount of deformation in the outer and inner circumferences of the bent portion may increase and the pipe may break. When the inner curvature radius value is equal to the pipe outer diameter, the deformation of the outer circumference and the inner circumference is about 25%, and it is possible to bend without damaging by appropriately selecting the heating conditions. There is no upper limit of the inner radius of curvature. Although the speed | rate of plastic deformation is not specifically limited, Generally, what is necessary is to carry out by applying a load over several hours in several minutes. If sudden deformation occurs, deterioration of the thermosetting resin may proceed.

The thermosetting resin curved pipe after plastic deformation to form the bent portion is quenched once to fix the structure. Since deformation can be performed even in a heated state, unnecessary deformation is likely to occur. Although it does not restrict | limit especially as a quenching method, For example, what is immersed in cold water is mentioned. Cooling is carried out until the pipe is at least at a temperature lower than Tg. In addition, in the case of using a suitable mold, it is not necessary to quench because unnecessary deformation does not occur.

After such plastic deformation, further undesired deformation can be prevented and completely cured by further hardening (heating for promoting a chemical reaction) at a high temperature. The curing conditions vary depending on the plastic strain temperature, but, for example, when a phenol resin is used, the temperature can be set to 180 to 350 ° C. for 10 to 100 hours in air.

Next, the process of carbonizing the mold release molded object made of a thermosetting resin is demonstrated.

In a carbonization process, the thermosetting resin mold release body obtained by the said plastic deformation process is carbonized, and it is made into a glassy carbon mold release molded body. As the carbonization treatment conditions, for example, heat treatment at a temperature of 800 to 2500 ° C. in a non-oxygen atmosphere (inert gas atmosphere or the like) is common.

As mentioned above, the glassy carbon shaped molded object of a desired shape can be obtained. For example, a contracted glassy carbon release tube having the same shape as the thermosetting resin release tube 3 shown in FIG. 2 can be obtained.

By the way, when obtaining a glass-shaped carbon release tube, in order to obtain a product with more dimensional accuracy, the core which has a carbonization shrinkage rate substantially the same as the thermosetting resin release tube used as a product (glass-like carbon release tube) precursor is used. It is preferable. In this case, the dimensions of the core may be substantially the same as at least part of the inner diameter (inner shape) of the product precursor. The reason is that the core also generates carbonization shrinkage in the same manner as the product precursor. This core has the effect of maintaining the product shape from the inside from the start to the end of the carbonization treatment.

Here, substantially "the same carbon shrinkage rate" means that the dimensional shrinkage percentage (%) before and after the carbonization treatment is within 2%, preferably within 1%. For example, carbonization of a 100 mm thermosetting resin molded product causes carbonization shrinkage to about 80% (slightly different depending on the resin). In this case, the shrinkage difference of 2% is the dimension difference of 2 mm. If less than this difference, it exhibits efficacy as a core. In large cases, the effect of maintaining its shape may not be sufficient, or the product (release glass tube made of glassy carbon) may be damaged.

On the other hand, the core is made of the same material and the carbonization shrinkage thereof is almost the same as that of the product, and the core is manufactured by combining two or more kinds of materials such as graphite and thermosetting resin, and the shrinkage ratio of the entire core is adjusted to the product. Can be obtained.

In addition, "substantially the same material" means the material of the same resin system. For example, when the glassy carbon release tube is a phenol resin, the core can use a low-cost foamed phenol resin having almost the same carbonization shrinkage ratio.

The core may have the same shape as that of the middle portion of the thermosetting resin tube, that is, a cross-section having a track shape or a four-cornered rectangular shape extending in the longitudinal direction of the mold tube, and may be a polygon extending in the longitudinal direction of the thermosetting resin tube. It is a rectangular shape extended in the longitudinal direction of the thermosetting resin release tube which has an arbitrary width and is the distance between the parallel planes of the release tube made of a thermosetting resin, and is arranged in multiple numbers in the cross-sectional longitudinal direction at arbitrary intervals between the parallel planes of the said thermosetting resin release tube. In this case, since the resin for the core is not required in a large amount and the removal becomes easy after carbonization, it is preferable.

Also, inserting a flexible material such as graphite felt or soft ceramic sheet between the core and the product is effective to prevent excessive contact between the core and the product, and furthermore, damage to the core.

In addition, the glassy carbon release tube may have a flange formed on one or both ends of the tube end, and a process for forming the flange will be described. Molding of the flange is a known method, for example the following three methods are used.

(1) press molding to injection molding

By using a flange-shaped mold, thermosetting resins such as phenol resins are formed under high pressure to form a flange portion. This is adhere | attached on the tube end of the thermosetting resin release tube which was already plastically deformed.

(2) mold molding

A liquid thermosetting resin is injected into a mold having a cavity of the flange portion, and a thermoset flange portion is formed. This flange part is bonded to the tube end part of the thermosetting resin mold release tube already plastically deformed. Alternatively, the flange portion can be integrated into the tube end of the thermosetting resin release tube by inserting a thermosetting resin release tube into the mold and then injecting and thermosetting the liquid thermosetting resin.

Adhesion between the flange portion and the release tube made of a thermosetting resin can be carried out using a known technique such as a method of using a liquid thermosetting resin as an adhesive, or a method of heating and melting a powder resin by applying a load to a joint part. In any of the above two methods, the flange portion, the release tube made of thermosetting resin, and the adhesive may be made of different thermosetting resins, but it is preferable to use the same resin so that the carbonization shrinkage is as close as possible to each other. In this way, a dimensional nonuniform change (decrease in precision) at the time of a carbonization process can be prevented.

When a glassy carbon tube is used as a chamber of a semiconductor manufacturing apparatus, a piping of a reaction vessel, or the like, since the glassy carbon tube is exposed to a corrosive environment, when a joint is present, the corrosion or strength of the portion becomes a problem. In particular, in the case of a glassy carbon release tube or a bent pipe, unlike the case of a circular cross section or a straight pipe, it is difficult to manufacture so that a junction part does not exist. However, the glassy carbon release molded article produced according to the above-described production method of the present invention may have no seams at the bent portion or no joint line in the direction parallel to the longitudinal direction of the tube, and thus has excellent corrosion resistance and strength. In addition, the glass-shaped carbon-formed release molded article produced in the present invention may not only form a track shape in cross section, but also arbitrarily produce a shape composed of a straight portion and a partial circle, for example, a four-cornered rectangular shape (see FIG. 5). Can be. In addition, it is also possible to easily manufacture a flange having a cross section in one direction or both cross sections of the release tube.

Next, the coupling | bonding structure of the connection member to the glassy carbon hollow molded object of this invention is demonstrated with reference to drawings. FIG. 7: is explanatory drawing which shows the coupling structure of the connection member to the glassy carbon hollow molded object which concerns on this invention, a is a front view, b is XX sectional enlarged view of a, FIG. 8 is a connection member shown in FIG. As explanatory drawing, a is a front view and b is a top view.

In the figure, 11 is a glass-shaped carbon hollow molded body, 12 is a connecting member, 13 is a sealing material, 14 is a holding member, and 15 is a fastening means. The hollow carbon molded body 11 made of glassy carbon is a glassy carbon shaped release tube formed of an ellipse in cross section in the present embodiment.

The connecting member 12 is integral with the sleeve 17 obtained by inserting inside the tube end (opening end) 16 of the glass-shaped carbon hollow molded body 11, and the outer periphery of the end of this sleeve 17. And the flange portion 18 is formed. Next, the groove 20 in which the elastic member 19 is mounted on the sleeve portion 17 side of the outer peripheral surface of the sleeve portion 17 and the intersection portion of the flange portion 18 is a hollow molded article made of glassy carbon ( The groove | channel 21 obtained by inserting the tube end part of the glass-shaped carbon hollow molded object 11 is formed in the flange part 18 in the specific part corresponding to the parallel surface of 11). Further, bolt holes 22 are formed at four corners of the flange portion 18. Moreover, as a material of the coupling member 12, it selects according to a use, such as glassy carbon, stainless steel, or quartz. In the present embodiment, the case where the elastic member 19 is mounted will be described as an example, and the mounting groove 20 will be described. However, a sleeve having a flat outer circumferential surface without the elastic member 19 and the mounting groove 20 will be described. 17).

The sealing material 13 uses an O-ring with a large deformed portion in this embodiment. In this way, even when the length of the glassy carbon hollow molded body 11 changes, the sealing surface slips, but the sealing property can be ensured.

The holding member 14 has a flat plate shape having the same shape as that of the flange portion 18, and has a through hole 23 obtained by inserting a glass-like carbon-shaped hollow molded body 11 into the outside thereof. On the flange part 18 side of 23, the V-shaped groove 24 which can push in the sealing material (O-ring) 13 between the flange parts 18 is formed. Further, bolt holes 25 are formed at four corners corresponding to the bolt holes 22 formed at the four corners of the flange portion 18. In addition, although these bolt holes 22 and 25 exist in four corners in this embodiment, according to the size and cross-sectional shape of the glass-shaped carbon hollow molded object 11, in consideration of sealing property, an appropriate number is formed in an appropriate position. Needless to say.

In the present embodiment, the fastening means 15 is provided with a bolt 26 and a nut 27, and the nut 27 is fastened to the bolt 26 to be fitted.

Bonding of the connection member 12 of the glassy carbon hollow molded object 11 using the said structural member is performed as follows. First, the retaining member 14 and the O-ring 13 are attached to the outer circumferential portion of the tube end portion of the glass-shaped carbon hollow molded body 11 and the mounting groove 20 of the sleeve portion 17 of the connecting member 12. An elastic member (for example, a string-like member made of the same material as the O-ring) 19 is mounted therein. Subsequently, the sleeve 17 of the connecting member 12 is inserted together with the elastic member 19 mounted in the mounting groove 20 in the tube end of the hollow glass molded body 11 of glassy carbon. The tube end of the molded body 11 is inserted until it fits into the groove 21 of the flange portion 18 of the connecting member 12. Thereafter, the bolt 26 of the fastening means 15 is inserted through the bolt hole 22 of the connecting member 12 and the bolt hole 24 of the retaining member 14 until the state described above is maintained to pass the bolt ( 27) Tighten. In this way, the O-ring 13 in the V-shaped groove 24 of the retaining member 14 is compressed between the flange 18 and pushes the tube end of the hollow glass shaped body 11 made of glassy carbon to engage.

As described above, since the coupling member 12 is coupled to the tube end of the hollow carbon-shaped hollow molded body 11, the O-ring 13 may be bonded to secure the sealing property. It is preferable to use a large deformed portion of the O-ring 13, and when the glass-shaped carbon hollow molded body 11 shrinks due to temperature change, the sealing surface of the O-ring 13 slides, but the deformed portion is large. It is possible to secure sealing property even if it shrinks by greatly deforming and sealing using the sealant. In addition, by loosening the bolt 26 of the fastening means 15 and removing the coupling, the connecting member 12 can be easily removed from the tube end of the glass-like carbon-shaped hollow molded body 11.

In addition, in the said embodiment, although the example which used the bolt 26 and the nut 27 as the fastening means 15 is demonstrated, in the state which overlapped the flange part 18 and the holding member 14 of the connection member 12, it is mentioned. The U-shaped clasp may be attached to the outer periphery thereof, and the U-shaped clasp may be fastened by bolts or wedges and the like.

Example

<Production of Glass Carbon Release Tubes>

(Example 1)

A commercially available liquid phenol resin (Resitop PL-4804 manufactured by Kunei Chemical Co., Ltd.) was heat-treated at 100 ° C. for 1 hour under reduced pressure, and the moisture content was adjusted to be a raw material of glassy carbon. This raw material was shape | molded by the centrifugal molding method using the centrifugal shaping | molding die of internal diameter 325mm x length 1600mm, and the round tube made of phenol resin of 320 mm in diameter and 3.5 mm in thickness was obtained. The glass transition point was 65 ° C.

The cylinder obtained above was cut to length 600mm. As shown in FIG. 1, two stainless pipes (rod-shaped jig) having an outer diameter of 60 mm x a length of 600 mm were placed in the cut cylinder. One bears the cylinder and the other is placed as a load on the bottom of the cylinder (see FIG. 1A). This form was heated at 90 degreeC for 5 hours, and the release pipe | tube made from the phenol resin of track shape in cross section was obtained (refer FIG. 1B). Subsequently, the phenol resin release tube was then carbonized by a conventional method to obtain a glassy carbon release tube having a diameter of a semicircle of the cross section of 48 mm, a length of the parallel portion of 340 mm, a total length of 480 mm, and no joint line in the longitudinal direction. Could.

(Example 2) Example when the flange is joined to the pipe end

By the same production method as in Example 1, a release cylinder made of a phenol resin having a track shape in cross section was obtained. On the other hand, a phenol resin tube having a thickness of 3 mm was formed by centrifugal molding using the same raw material as in Example 1, and the molded body was cut to obtain a phenol resin plate having a thickness of 3 mm. From this plate, a resin plate on a track-shaped donut was cut out having a hole equal to the outer shape of the track-shaped releasing cylinder made of the track-shaped phenol resin at the center of the width 86 mm x the parallel part 425 mm x the circular part 33 mm. The two parts were bonded to the phenol resin and carbonized in the same manner as in Example 1 to obtain a cylindrical section of 48 mm in diameter, a parallel section of 340 mm, and a total length of 480 mm. A glassy carbon shaped release tube having an 8 mm flange could be obtained.

(Example 3) Example of using a core

Commercially available liquid phenolic resin (recipe top manufactured by Kunei Chemical Co. PL-4804) was heat-treated at 100 ° C. for 1 hour under reduced pressure, and the moisture content was adjusted to be a raw material of glassy carbon. This raw material was shape | molded by the centrifugal molding method using the centrifugal shaping | molding die of internal diameter 325mm x length 1600mm, and the cylinder of phenol resin of 320 mm in diameter and 3.5 mm in thickness was obtained.

The cylinder obtained above was cut to length 500mm. As shown in FIG. 1, two stainless pipes (rod-shaped jig) having an outer diameter of 60 mm x a length of 600 mm were placed in the cut cylinder. One bears the cylinder and the other is placed as a load on the bottom of the circular tube (see FIG. 1A). In this state, it heated at 90 degreeC for 5 hours, and the release cylinder tube made of the phenol resin of track shape of a cross section was obtained (refer FIG. 1B).

Eight phenol resin plates of thickness 3mm x width 60mmx length 500mm were inserted in the inside of the said phenol resin release circular tube at predetermined space | interval as shown in FIG. Thereafter, this phenol resin release cylinder was heat-treated at 1000 ° C. in an inert atmosphere to carbonize to obtain a glassy carbon release tube. The obtained glassy carbon release tube is suited as a semiconductor manufacturing apparatus chamber within ± 0.6 mm with respect to an average value of 48 mm of parallel part spacing. 3A shows the carbonization treatment before and FIG. 3B shows the carbonization treatment. In addition, in the figure, 4 is a mold release cylinder made of phenol resins, 5 is a phenol resin board, and 6 shows a glass-shaped carbon release tube.

Further, for comparison, a graphite core 7 formed into a rectangle having a thickness of 48 mm x 320 mm x 400 mm in length is inserted into the phenol resin release cylinder 4 as shown in FIG. In the same manner, the phenol resin release cylinder 4 was heat-treated at 1000 ° C. in an inert powder and carbonized to obtain a glassy carbon release tube 8. The obtained glassy carbon release tube 8 is not satisfactory for use as a semiconductor manufacturing apparatus chamber because the width of the parallel portion varies by ± 1.6 mm with respect to an average value of 45 mm.

<Manufacture of bend pipes>

(Example 4)

The commercial liquid phenol resin PL-4804 manufactured by Gunney Chemical was heat-treated at 100 ° C. for 1 hour, and the moisture content was adjusted to obtain a glassy carbon raw material resin. 90 g of the glassy carbon raw material resin was put into a cylindrical centrifugal mold having an inner diameter of 12 mm and a length of 1000 mm, and the cylindrical centrifugal mold was centrifuged at a surface temperature of 90 ° C. for 5 hours while rotating the cylindrical centrifugal mold at a speed of 500 minutes per minute. The result was a thermosetting resin pipe 41 having a straight tube having an outer diameter of 12 mm, a length of 950 mm, and a thickness of 2.5 mm (see FIG. 10A). Tg of this thermosetting resin pipe 41 was 55 degreeC.

The thermosetting resin pipe 41 was filled with sea sand 42 (particle diameter 300 to 600 µm) manufactured by Waco Pure Chemical Co., and the pipe end was closed with cotton 43 (see FIG. 10B). Subsequently, while heating an area of 8 to 12 cm from one end of the pipe 41 at 80 ° C., the part is bent and plastically deformed to have an inner curvature radius of 15 mm to form an L-shaped bent pipe shape, and the shape is maintained. While being immersed in cold water and cooled to fix the curved structure, a curved pipe 44 made of a thermosetting resin having a bent portion was used (see FIG. 10C). After quenching with cold water, the charged sea sand 42 was removed.

Next, in this thermosetting resin-made bending pipe 44, it heated up to 250 degreeC at the temperature increase rate of 2 degree-C / min in air atmosphere, it preserve | saved at this temperature for 50 hours, and completely hardened. Thereafter, the thermosetting resin bent pipe 44 was heated and carbonized at 1000 ° C. for 5 hours in a nitrogen atmosphere to obtain a glassy carbon bent pipe having a bent portion. The outer diameter of this glassy carbon bent pipe was 10 mm and the thickness was 2 mm.

(Comparative Example 1)

Using a thermosetting resin pipe obtained in the same manner as in Example 4, under the same conditions, the plastic sheet was subjected to plastic deformation by bending without filling seaweed. As a result, it deformed to 1 mm or less in the place where the internal part of a hollow part of a bend part was narrow, and it could not be used as a piping component.

(Comparative Example 2)

Using a thermosetting resin pipe obtained in the same manner as in Example 4, under the same conditions, except that the heating temperature is plastically deformed at 60 ° C. below the lower limit temperature (Tg + 10 ° C.) specified in the present invention and bent. Processed. As a result, a crack occurred in the pipe and was broken before applying the force to obtain the desired deformation amount.

(Comparative Example 3)

Using the thermosetting resin pipe obtained by the method similar to Example 4, it was made into the same conditions except that the heating temperature was bent to 160 degreeC exceeding the upper limit temperature 150 degreeC prescribed | regulated by this invention, and processing started. As a result, although the thermosetting resin pipe softened once, hardening reaction advanced rapidly and further plastic deformation became impossible before the desired amount of deformation was obtained.

According to the method for producing a glassy carbon release molded article according to the present invention, a cylindrical tubular molded article made of a thermosetting resin is used to release a glassy carbon component or a curved pipe having a release tubular shape, typically an ellipse, a partial circle, and a straight section. Can be manufactured with high precision and relatively easy. In addition, a glass-shaped carbon release tube or a bent pipe excellent in corrosion resistance and strength can be produced by using a cylindrical molded body of thermosetting resin having no joint line in a direction parallel to the axial direction of the cylindrical molded body. In addition, the glassy carbon release pipe or the bent pipe made of no joining portion in this manner has excellent corrosion resistance and strength compared to the presence of the joining portion, and is easy to be applied to a chamber of a semiconductor manufacturing apparatus in which the glassy carbon tube is exposed to a corrosive environment.

Moreover, according to the coupling structure of the connection member to the glass shaped carbon hollow molded object which concerns on this invention, it installs by connecting another member to the opening edge part of the glass shaped carbon molded object of cross section other than a thin thickness or circular shape whose strength is not enough. A connecting member such as a flange or a connecting member as a cover can be provided with good sealing properties while being removable. Moreover, since the sealing of a connection part is ensured with the outer peripheral sealing material (O-ring etc.) of the opening edge part of a hollow carbonaceous member, airtightness can be maintained even if a hollow glassy carbon molded object expands length or thickness under use conditions.

Claims (5)

A coupling structure in which a coupling member is coupled to an opening end of a hollow glass-shaped carbon release tube and installed, wherein the flange member is integrally formed on the outer circumference of a sleeve portion that can be inserted inside the glass-like carbon release tube and glassy carbon. A sealing member disposed on the outer circumference of the opening end of the release tube and a holding member for holding the sealing member between the flange portion of the connecting member are provided, and the holding member is flanged via a fastening means. A coupling structure of a connecting member to a glassy carbon shaped release tube, wherein the sealing member held in between the retaining member and the flange portion is fastened to and coupled to the opening member of the glassy carbon shaped release tube. The method of claim 1, An elastic member is disposed on at least a portion of an outer circumferential surface of a sleeve portion to be inserted inside a glass-shaped carbon molded body. The method of claim 1, A coupling structure of a connecting member to a glass-shaped carbon release tube, wherein the glass-shaped carbon release tube has a shape in which a long cross section, an ellipse, or a parallel straight line having a cross-section perpendicular to the hollow direction is curved. The method of claim 1, A coupling structure of a coupling member to a glassy carbon shaped release tube, wherein the coupling member and the retention member are made of metal or ceramic. A coupling structure in which a coupling member is coupled to an opening end of a hollow glass-shaped carbon molded body, the coupling member being formed integrally with a flange portion on an outer circumference of a sleeve that can be inserted into the glass-shaped carbon molded body, and a glass-shaped carbon molded body. A sealing member disposed on the outer periphery of the opening end, and a retaining member for sandwiching the sealing member between the flange portion of the connecting member and the retaining member. And an opening end of the glassy carbon molded body and the coupling member by compressing a sealing material held between the flange and the flange portion. The coupling structure of the connecting member to the glassy carbon molded body characterized by the above-mentioned.

Images